US6274760B1ExpiredUtility

Preparation of formylphosphonic acid from tertiary aminomethylphosphonic acid N-oxides

Assignee: MONSANTO COPriority: Mar 14, 2000Filed: Mar 14, 2000Granted: Aug 14, 2001

Est. expiryMar 14, 2020(expired)· nominal 20-yr term from priority

Inventors:Thaddeus S. Franczyk, Ii

C07F 9/3891C07F 9/3813C07F 9/3817

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120

Claims

Abstract

Formylphosphonic acid derivatives are prepared by the catalytic decomposition of a (phosphonomethyl)amine N-oxide compound to form the formylphosphonic acid derivative and a dephosphonomethylated amine.

Claims

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What is claimed is:

1. A process for preparing a formylphosphonic acid derivative, said process comprising decomposing a (phosphonomethyl)amine N-oxide compound in the presence of a decomposition catalyst to produce said formylphosphonic acid derivative and a dephosphonomethylated amine.

2. The process of claim 1 wherein said formylphosphonic acid derivative has a structure of formula (I):
said (phosphonomethyl)amine N-oxide compound has a structure of formula (II):
said dephosphonomethylated amine has a structure of formula (III):
and wherein:
R 1 and R 2 are independently selected from the group consisting of H, hydrocarbyl, substituted hydrocarbyl, heterocycle, and a salt-forming cation, and R 1 and R 2 taken together with the oxygen and phosphorus atoms to which they are attached optionally form a cyclic structure;
R 3 is selected from the group consisting of —CHO and —CH(OR 8 )(OR 9 );
R 4 and R 5 are independently selected from the group consisting of H, —CH 2 PO(OR 6 )(OR 7 ), hydrocarbyl, substituted hydrocarbyl, and heterocycle, and R 4 and R 5 taken together with the nitrogen atom to which they are attached optionally form a cyclic structure;
R 6 and R 7 are independently selected from the group consisting of H, hydrocarbyl, substituted hydrocarbyl, heterocycle, and a salt-forming cation, and R 6 and R 7 taken together with the oxygen and phosphorus atoms to which they are attached optionally form a cyclic structure; and
R 8 and R 9 are independently selected from the group consisting of H, hydrocarbyl, substituted hydrocarbyl, and heterocycle, and R 8 and R 9 taken together with the oxygen and carbon atoms to which they are attached optionally form a cyclic structure.

3. The process of claim 2 wherein the temperature is in the range of about 0° C. to about 150° C.

4. The process of claim 3 wherein the temperature is in the range of about 20° C. to about 110° C.

5. The process of claim 4 wherein the temperature is in the range of about 20° C. to about 75° C.

6. The process of claim 2 wherein said (phosphonomethyl)amine N-oxide is decomposed under neutral or acidic conditions.

7. The process of claim 6 wherein decomposition of said (phosphonomethyl)amine N-oxide compound is performed at about pH 3 or less.

8. The process of claim 2 further comprising reacting said dephosphonomethylated amine under phosphonomethylation conditions to produce a (phosphonomethyl)amine compound and oxidizing said (phosphonomethyl)amine compound to regenerate said (phosphonomethyl)amine N-oxide compound.

9. The process of claim 8 wherein said phosphonomethylation conditions comprise reacting said dephosphonomethylated amine in the presence of phosphorus trichloride, water, and a source of formaldehyde to produce said (phosphonomethyl)amine compound.

10. The process of claim 8 wherein said phosphonomethylation conditions comprise reacting said dephosphonomethylated amine in the presence of phosphorous acid, a strong mineral acid, and a source of formaldehyde to produce said (phosphonomethyl)amine compound.

11. The process of claim 2 wherein at least one of R 4 and R 5 is —CH 2 PO(OR 6 )(OR 7 ).

12. The process of claim 11 wherein one of R 4 and R 5 is —CH 2 PO(OR)(OR 7 ) and the other of R 4 and R 5 is 2-hydroxyethyl.

13. The process of claim 2 wherein R 4 and R 5 are independently selected from the group consisting of —CH 2 PO(OR 6 )(OR 7 ) and hydrocarbyl.

14. The process of claim 13 wherein R 4 and R 5 are both —CH 2 PO(OR 6 )(OR 7 ).

15. The process of claim 13 wherein R 4 and R 5 are both hydrocarbyl.

16. The process of claim 13 wherein one of R 4 and R 5 is hydrocarbyl and the other of R 4 and R 5 is —CH 2 PO(OR 6 )(OR 7 ).

17. The process of claim 2 wherein the decomposition catalyst comprises a metal.

18. The process of claim 17 wherein the decomposition catalyst comprises a metal selected from the group consisting of iron, zinc, aluminum, vanadium, molybdenum, and copper.

19. The process of claim 18 wherein the metal is in a zero valence state.

20. The process of claim 18 wherein the metal is in a metallic form.

21. The process of claim 18 wherein the metal is in a salt or an oxide form.

22. The process of claim 18 wherein the decomposition catalyst comprises a compound selected from the group consisting of a vanadium salt, an iron salt, and a copper salt.

23. The process of claim 18 wherein the decomposition catalyst comprises a compound selected from the group consisting of vanadium pentoxide, vanadyl sulfate, vanadium chloride, ferrous sulfate, ferrous chloride, and ferrous bromide.

24. The process of claim 23 wherein the decomposition catalyst comprises a compound selected from the group consisting of vanadium pentoxide, vanadyl sulfate, and vanadium chloride.

25. The process of claim 24 wherein the decomposition catalyst comprises vanadyl sulfate.

26. The process of claim 18 wherein the decomposition catalyst comprises a water-soluble decomposition catalyst.

27. The process of claim 2 conducted in a continuous reaction zone into which said (phosphonomethyl)amine N-oxide compound is continuously or intermittently introduced and from which a reaction product mixture comprising said formylphosphonic acid derivative is continuously or intermittently withdrawn.

28. The process of claim 2 wherein said (phosphonomethyl)amine N-oxide compound is prepared by oxidizing a (phosphonomethyl)amine compound with a peroxide in the presence of an oxidation catalyst to produce said (phosphonomethyl)amine N-oxide.

29. The process of claim 28 wherein said (phosphonomethyl)amine compound is nitrilotris(methylenephosphonic acid).

30. The process of claim 28 wherein said peroxide is selected from the group consisting of hydrogen peroxide, performic acid, peracetic acid, perbenzoic acid, peroxytrifluoroacetic acid, benzoyl peroxide, benzenepersulfonic acid, and combinations thereof.

31. The process of claim 30 wherein said peroxide comprises hydrogen peroxide.

32. The process of claim 28 wherein said oxidation catalyst comprises a metal.

33. The process of claim 32 wherein said oxidation catalyst comprises a transition metal.

34. The process of claim 33 wherein said oxidation catalyst comprises a transition metal selected from the group consisting of molybdenum, tungsten, cobalt, silver, iron, nickel, chromium, ruthenium, vanadium, cerium, manganese, and salts and complexes thereof.

35. The process of claim 34 wherein said oxidation catalyst comprises a transition metal selected from the group consisting of tungsten, cobalt, vanadium, cerium, manganese, and salts and complexes thereof.

36. The process of claim 35 wherein said oxidation catalyst comprises a transition metal selected from the group consisting of tungsten, cobalt, vanadium, and salts and complexes thereof.

37. The process of claim 36 wherein said oxidation catalyst comprises tungsten or a salt or complex thereof.

38. The process of claim 37 wherein said oxidation catalyst comprises sodium tungstate.

39. The process of claim 34 wherein said oxidation catalyst comprises molybdenum.

40. The process of claim 39 wherein the reaction mixture further comprises a metabisulfite compound.

41. The process of claim 40 wherein said metabisulfite compound comprises sodium metabisulfite.

42. The process of claim 32 wherein said oxidation catalyst comprises a metal selected from the group consisting of aluminum, tin, lead, and salts and complexes thereof.

43. The process of claim 2 wherein the decomposition is performed in the presence of a solvent.

44. The process of claim 43 wherein said solvent comprises a material selected from the group consisting of water and an organic solvent.

45. The process of claim 44 wherein said solvent comprises an organic solvent.

46. The process of claim 45 wherein said organic solvent comprises an alcohol.

47. The process of claim 46 wherein said alcohol is selected from the group consisting of aliphatic alcohols, aromatic alcohols, glycols, polyols, and unsaturated alcohols.

48. The process of claim 44 wherein said solvent comprises water.

49. The process of claim 28 wherein the oxidation of said (phosphonomethyl)amine compound to said (phosphonomethyl)amine N-oxide compound and the decomposition of said (phosphonomethyl)amine N-oxide compound to said formylphosphonic acid derivative and said dephosphonomethylated amine is performed in a single vessel.

50. The process of claim 49 wherein said oxidation catalyst comprises said decomposition catalyst.

51. The process of claim 50 wherein said oxidation catalyst comprises a compound selected from the group consisting of vanadium metal, a vanadium salt, and an oxide of vanadium.

52. The process of claim 50 wherein said oxidation catalyst comprises vanadyl sulfate.

53. The process of claim 28 wherein the oxidation of said (phosphonomethyl)amine compound to said (phosphonomethyl)amine N-oxide compound and the decomposition of said (phosphonomethyl)amine N-oxide compound to said formylphosphonic acid derivative and said dephosphonomethylated amine are performed in two or more steps.

54. A process for preparing formylphosphonic acid or a salt or a hydrate thereof, said process comprising oxidizing nitrilotris(methylenephosphonic acid) or a salt thereof to form nitrilotris(methylenephosphonic acid) N-oxide or a salt thereof, and decomposing said nitrilotris(methylenephosphonic acid) N-oxide or salt thereof in the presence of a decomposition catalyst to form formylphosphonic acid or a salt thereof.

55. The process of claim 54 wherein the oxidation of nitrilotris(methylenephosphonic acid) comprises contacting nitrilotris(methylenephosphonic acid) with a peroxide in the presence of an oxidation catalyst.

56. The process of claim 55 wherein said peroxide comprises hydrogen peroxide.

57. The process of claim 55 wherein said oxidation catalyst comprises a metal.

58. The process of claim 57 wherein said oxidation catalyst comprises a transition metal.

59. The process of claim 58 wherein said oxidation catalyst comprises a transition metal selected from the group consisting of molybdenum, tungsten, cobalt, silver, iron, nickel, chromium, ruthenium, vanadium, cerium, manganese, and salts and complexes thereof.

60. The process of claim 59 wherein said oxidation catalyst comprises a transition metal selected from the group consisting of tungsten, cobalt, vanadium, cerium, manganese, and salts and complexes thereof.

61. The process of claim 60 wherein said oxidation catalyst comprises a transition metal selected from the group consisting of tungsten, cobalt, vanadium, and salts and complexes thereof.

62. The process of claim 61 wherein said oxidation catalyst comprises tungsten or a salt or complex thereof.

63. The process of claim 62 wherein said oxidation catalyst comprises sodium tungstate.

64. The process of claim 59 wherein said oxidation catalyst comprises molybdenum.

65. The process of claim 64 wherein the reaction mixture further comprises a metabisulfite compound.

66. The process of claim 65 wherein said metabisulfite compound comprises sodium metabisulfite.

67. The process of claim 57 wherein said oxidation catalyst comprises a metal selected from the group consisting of aluminum, tin, lead, and salts and complexes thereof.

68. The process of claim 54 wherein said decomposition catalyst comprises a metal.

69. The process of claim 68 wherein said decomposition catalyst comprises a metal selected from the group consisting of iron, zinc, aluminum, vanadium, molybdenum, and copper.

70. The process of claim 69 wherein the metal is in a zero valence state.

71. The process of claim 70 wherein the metal is in a metallic form.

72. The process of claim 69 wherein the metal is in a salt or an oxide form.

73. The process of claim 72 wherein the decomposition catalyst comprises a compound selected from the group consisting of a vanadium salt, an iron salt, and a copper salt.

74. The process of claim 69 wherein the decomposition catalyst comprises a compound selected from the group consisting of vanadium pentoxide, vanadyl sulfate, vanadium chloride, ferrous sulfate, ferrous chloride, and ferrous bromide.

75. The process of claim 74 wherein said decomposition catalyst comprises a compound selected from the group consisting of vanadium pentoxide, vanadyl sulfate, and vanadium chloride.

76. The process of claim 75 wherein said decomposition catalyst comprises vanadyl sulfate.

77. The process of claim 69 wherein said decomposition catalyst comprises a water-soluble decomposition catalyst.

78. The process of claim 54 wherein said decomposition is performed at a temperature in the range of about 0° C. to about 150° C.

79. The process of claim 78 wherein said decomposition is performed at a temperature in the range of about 20° C. to about 110° C.

80. The process of claim 79 wherein said decomposition is performed at a temperature in the range of about 20° C. to about 75° C.

81. The process of claim 54 wherein said (phosphonomethyl)amine N-oxide is decomposed under neutral or acidic conditions.

82. The process of claim 81 wherein decomposition of said (phosphonomethyl)amine N-oxide is performed at about pH 3 or less.

83. The process of claim 54 wherein said decomposition is performed in the presence of a solvent.

84. The process of claim 83 wherein said solvent comprises a material selected from the group consisting of water and an organic solvent.

85. The process of claim 84 wherein said solvent comprises an organic solvent.

86. The process of claim 85 wherein said organic solvent comprises an alcohol.

87. The process of claim 86 wherein said alcohol is selected from the group consisting of aliphatic alcohols, aromatic alcohols, glycols, polyols, and unsaturated alcohols.

88. The process of claim 84 wherein said solvent comprises water.

89. The process of claim 54 wherein the oxidation of said (phosphonomethyl)amine compound to said (phosphonomethyl)amine N-oxide compound and the decomposition of said (phosphonomethyl)amine N-oxide compound to said formylphosphonic acid derivative and said dephosphonomethylated amine are performed in a single vessel.

90. The process of claim 89 wherein said oxidation catalyst comprises said decomposition catalyst.

91. The process of claim 90 wherein said oxidation catalyst comprises a compound selected from the group consisting of vanadium, a vanadium salt, and a vanadium oxide.

92. The process of claim 90 wherein said oxidation catalyst comprises vanadyl sulfate.

93. The process of claim 54 wherein the oxidation of said (phosphonomethyl)amine compound to said (phosphonomethyl)amine N-oxide compound and the decomposition of said (phosphonomethyl)amine N-oxide compound to said formylphosphonic acid derivative and said dephosphonomethylated amine are performed in two or more steps.

94. A process for preparing N-(phosphonomethyl)glycine, or a salt or an ester thereof, wherein said process comprises decomposing a (phosphonomethyl)amine N-oxide compound in the presence of a decomposition catalyst to produce a formylphosphonic acid derivative and a dephosphonomethylated amine, and reacting said formylphosphonic acid derivative to produce N-(phosphonomethyl)glycine, or a salt or an ester thereof, wherein:
said formylphosphonic acid derivative has a structure of formula (I):
said (phosphonomethyl)amine N-oxide compound has a structure of formula (II):
said dephosphonomethylated amine has a structure of formula (III):
and wherein:
R 1 and R 2 are independently selected from the group consisting of H, hydrocarbyl, substituted hydrocarbyl, heterocycle, and a salt-forming cation, and R 1 and R 2 taken together with the oxygen and phosphorus atoms to which they are attached optionally form a cyclic structure;
R 3 is selected from the group consisting of —CHO and —CH(OR 8 )(OR 9 );
R 4 and R 5 are independently selected from the group consisting of H, —CH 2 PO(OR 6 )(OR 7 ), hydrocarbyl, substituted hydrocarbyl, and heterocycle, and R 4 and R 5 taken together with the nitrogen atom to which they are attached optionally form a cyclic structure;
R 6 and R 7 are independently selected from the group consisting of H, hydrocarbyl, substituted hydrocarbyl, heterocycle, and a salt-forming cation, and R 6 and R 7 taken together with the oxygen and phosphorus atoms to which they are attached optionally form a cyclic structure; and
R 8 and R 9 are independently selected from the group consisting of H, hydrocarbyl, substituted hydrocarbyl, and heterocycle, and R 8 and R 9 taken together with the oxygen and carbon atoms to which they are attached optionally form a cyclic structure.

95. The process of claim 94 wherein the reaction of said formylphosphonic acid derivative to produce N-(phosphonomethyl)glycine comprises condensing said formylphosphonic acid derivative with a glycine compound having a structure of formula (XI)
or a zwitterion thereof to form a condensed carboxylate intermediate, and reducing said condensed carboxylate intermediate to produce N-(phosphonomethyl)glycine or a salt or an ester thereof, wherein R 10 is selected from the group consisting of H, hydrocarbyl, substituted hydrocarbyl, heteroaryl, and a salt-forming cation.

96. The process of claim 95 wherein the reduction of said condensed carboxylate intermediate comprises reacting said condensed carboxylate intermediate in the presence of hydrogen and a hydrogenation catalyst.

97. The process of claim 96 wherein said hydrogenation catalyst comprises a noble metal.

98. The process of claim 97 wherein said hydrogenation catalyst comprises a noble metal selected from the group consisting of platinum, palladium, nickel, and copper.

99. The process of claim 98 wherein said hydrogenation catalyst comprises Raney nickel.

100. The process of claim 98 wherein said hydrogenation catalyst further comprises a solid support.

101. The process of claim 100 wherein said solid support comprises a carbon solid support.

102. The process of claim 101 wherein said hydrogenation catalyst comprises palladium on carbon.

103. The process of claim 94 wherein the reaction of said formylphosphonic acid derivative to produce N-(phosphonomethyl)glycine comprises condensing said formylphosphonic acid derivative with 1-amino-2-hydroxyethane to form a condensed alcohol intermediate, reducing said condensed alcohol intermediate to produce an N-(2-hydroxyethyl)-N-(phosphonomethyl)amine compound having a structure of formula (X)
or a zwitterion thereof, and oxidizing said N-(2-hydroxyethyl)-N-(phosphonomethyl)amine compound to produce N-(phosphonomethyl)glycine or a salt or an ester thereof, wherein:
R 1 and R 2 are independently selected from the group consisting of H, hydrocarbyl, substituted hydrocarbyl, heterocycle, and a salt-forming cation, and R 1 and R 2 taken together with the oxygen and phosphorus atoms to which they are attached optionally form a cyclic structure; and
R 10 is selected from the group consisting of is selected from the group consisting of H, hydrocarbyl, substituted hydrocarbyl, heteroaryl, and a salt-forming cation.

104. The process of claim 103 wherein the reduction of said condensed alcohol intermediate comprises reacting said condensed alcohol intermediate in the presence of hydrogen and a hydrogenation catalyst.

105. The process of claim 104 wherein said hydrogenation catalyst comprises a noble metal.

106. The process of claim 105 wherein said hydrogenation catalyst comprises a noble metal selected from the group consisting of platinum, palladium, nickel, and copper.

107. The process of claim 106 wherein said hydrogenation catalyst comprises Raney nickel.

108. The process of claim 106 wherein said hydrogenation catalyst further comprises a solid support.

109. The process of claim 108 wherein said solid support comprises a carbon solid support.

110. The process of claim 109 wherein said hydrogenation catalyst comprises palladium on carbon.

111. The process of claim 103 wherein the oxidation of said N-(2-hydroxyethyl)-N-(phosphonomethyl)amine compound comprises dehydrogenation.

112. The process of claim 94 wherein the formylphosphonic acid derivative is condensed with a source of ammonia to form an ammonia-formylphosphonic condensate compound, reducing the ammonia-formylphosphonic condensate compound to form an aminomethylphosphonic acid compound having a structure of formula (XIII)
or a zwitterion thereof, and reacting the aminomethylphosphonic acid compound to produce N-(phosphonomethyl)glycine or a salt or an ester thereof, wherein R 1 and R 2 are independently selected from the group consisting of H, hydrocarbyl, substituted hydrocarbyl, heterocycle, and a salt-forming cation, and R 1 and R 2 taken together with the oxygen and phosphorus atoms to which they are attached optionally form a cyclic structure.

113. The process of claim 112 wherein the reduction of said ammonia-formylphosphonic condensate compound comprises reacting said ammonia-formylphosphonic condensate compound in the presence of hydrogen and a hydrogenation catalyst.

114. The process of claim 113 wherein said hydrogenation catalyst comprises a noble metal.

115. The process of claim 114 wherein said hydrogenation catalyst comprises a noble metal selected from the group consisting of platinum, palladium, nickel, and copper.

116. The process of claim 115 wherein said hydrogenation catalyst comprises Raney nickel.

117. The process of claim 115 wherein said hydrogenation catalyst further comprises a solid support.

118. The process of claim 117 wherein said solid support comprises a carbon solid support.

119. The process of claim 118 wherein said hydrogenation catalyst comprises palladium on carbon.

120. The process of claim 112 wherein the oxidation of said N-(2-hydroxyethyl)-N-(phosphonomethyl)amine compound comprises dehydrogenation.

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